CN108417811A - A kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material and its synthetic method - Google Patents
A kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material and its synthetic method Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/5815—Sulfides
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material and its synthetic methods, it is related to micro-nano material synthesis field, the sandwich layer of the composite material is the ternary ferrimanganic sulfide of club shaped structure, the ternary ferrimanganic sulfide is coated with graphene layer, and it is connected through graphene layer between the ternary ferrimanganic sulfide of club shaped structure, ternary ferrimanganic sulfide corresponds to is not coated with carbon coating layer by the position that graphene layer coats, composite material is under the double action of graphene layer and carbon coating layer, form complete conductive network, the stomata of connection ternary ferrimanganic sulfide is distributed in the surface of the graphene layer.The composite material of preparation can form a complete conductive network under the double action of graphene and carbon coating layer；The stomata that graphene surface is generated with potassium hydroxide high-temperature heat treatment simultaneously enables each rodlike composite material to reserve enough channels in electrochemical reaction so that electrolyte infiltration and ion are transmitted.
Description
Technical field
The present invention relates to micro-nano materials to synthesize field, and in particular to a kind of carbon coating club shaped structure ternary ferrimanganic sulfide stone
Black alkene composite material and its synthetic method.
Background technology
The new carbon that graphene was just found as 2004, is the most thin material found so far.Graphene shows
Go out the excellent properties such as strong electric conductivity, superpower hardness and toughness, extra specific surface area, special thermal conductivity and high transparency so that
Graphene becomes a kind of ideal basis material.In order to further widen the application field of graphene, researcher will
Graphene and many functional materials are compound, and the graphene-based composite material with abundant structure, composition and property is prepared,
These composite materials can be widely applied to the fields such as catalysis, sensing, photoelectricity, medicine and energy storage.
Iron ore, manganese ore are in nature rich reserves, and classes of compounds is various, cheap, non-hazardous to environment, always
Since be all important research object as electrochemical energy storage, and the combination of iron ore, manganese ore and graphene is also always to receive row
Favor in the industry.
Such as Chinese patent (106981636 A of CN), using solvent-thermal method, waits for third using ferric acetyl acetonade, acetone as solvent
Freeze-drying obtains FeS/RGO presomas after ketone volatilization completely；Then using thiocarbamide as sulphur source, using high temperature vulcanized in graphene
Area load FeS has synthesized the negative material that binary FeS/RGO composite materials are used as sodium-ion battery, FeS particles or lamella
It is anchored on graphene sheet layer, the electric conductivity of FeS is improved using graphene, improve high rate performance, show good electrochemistry
Performance,.
For another example, it is small to react 18-20 by hydro-thermal process at 160-260 DEG C first for Chinese patent (106159239 A of CN)
At present three-dimensional column redox graphene is prepared, then with manganese chloride, manganese sulfate, manganese nitrate etc. for manganese source, with thioacetyl
Amine, thiocarbamide are sulphur source, and three-dimensional redox graphene is template, and two kinds of mixture in ethylene glycol, ethyl alcohol, isopropanol is molten
Agent；Group on wherein three-dimensional redox graphene is by the negative ions in adsorbent solution, by solvent-thermal process so that sulphur
Changing manganese, directly progress growth in situ prepares manganese sulfide/graphene composite material nano particle on the surface of graphene, passes through preparation
Three-dimensional column redox graphene improves stability difference caused by volume change of the manganese sulfide in electrochemical reaction process
Disadvantage.
But above two technologies, the material that the former prepares, with the progress of the electrochemical reaction of material, FeS particles or
Lamella can because sodium ion insertion abjection process, inevitably make material volume expand or dusting and from graphene sheet layer
On fall off, eventually lead to the decline of its chemical property；And the latter prepare composite material, according to its scanning electron microscope (SEM) photograph it is found that
The size of the composite material is nano-scale particle, and there are serious agglomeration phenomenons for nano particle composite material, to it can cause after
The performance of phase declines apparent.
Invention content
A kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material of present invention offer and its synthetic method,
With solve graphene composite material prepared by existing preparation method after use the phase because the reason of material physical property itself, makes
Chemical property declines serious technical problem.
The purpose of the present invention can be realized by technical solution below：
The sandwich layer of a kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, the composite material is stick
The ternary ferrimanganic sulfide of shape structure, the ternary ferrimanganic sulfide are coated with graphene layer, and three rod iron of club shaped structure
It is connected through graphene layer between manganese sulfide, ternary ferrimanganic sulfide corresponds to is not coated with carbon packet by the position that graphene layer coats
Coating, composite material form complete conductive network, the graphene layer under the double action of graphene layer and carbon coating layer
Surface be distributed with connection ternary ferrimanganic sulfide stomata.
Preferably, the ternary ferrimanganic sulfide of the club shaped structure is nanometer rods, and the length of nanometer rods is 100nm-5
μm, nanometer rods width is 10nm-1 μm.
A kind of synthetic method of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, including walk as follows
Suddenly：
1) graphene and potassium hydroxide are mixed evenly in tube furnace, in 350-800 DEG C of pyroreaction by graphite
Alkene is configured to graphene solution, in pyroreaction, graphene react at high temperature with potassium hydroxide generate potassium carbonate and
Hydrogen, further potassium carbonate decomposes and generates carbon dioxide at high temperature, and the graphene surface after two step pyroreactions is just
It will produce stomata；
2) ferric nitrate, manganese nitrate solution are then measured, graphene solution is added, is sufficiently stirred 10min；
3) it weighs in the above-mentioned mixed solution of ammonium fluoride solid addition and stirs 10min；
4) it weighs in the above-mentioned mixed solution of urea addition and stirs 20min；
5) aforesaid liquid is transferred in reaction kettle or other corresponding vessel and is sealed；
6) reactions such as hydro-thermal or water-bath, reaction time 5-24h are carried out at 90-200 DEG C；
7) taking precipitate is filtered washing or centrifuge washing；
8) it weighs deionized water and product that thioacetamide obtains in 7), is sufficiently stirred 20min；
9) 8) liquid obtained is transferred in reaction kettle or other corresponding vessel and is sealed；
10) reactions such as hydro-thermal or water-bath, reaction time 5-24h are carried out at 90-200 DEG C；
11) taking precipitate is filtered washing or centrifuge washing obtains clean product, you can obtains club shaped structure ternary
Ferrimanganic sulfur graphite ene compound composite material；
12) in 300-800 DEG C of N21-5h high temperature sintering carbon coatings are carried out under environment, obtain carbon coating club shaped structure ternary
Ferrimanganic sulfide graphene composite material.
As priority, in the step 1) graphene solution a concentration of 0.1-3g/L.
As priority, in the step 2) ferric nitrate, manganese nitrate solution, Fe3+Mole be Mn2+1-6 times,
A concentration of 0.1-5mol/L of middle ferric nitrate.
As priority, in step 3), after ammonium fluoride solid is added in mixed solution, fluorination ammonium concentration is maintained at 0.01-
3mol/L。
As priority, in step 4), after urea is added in mixed solution, the concentration of urea is maintained at 0.01-5mol/L.
As priority, the material of step 5), step 9) reaction kettle or other corresponding vessel is polytetrafluoroethylene (PTFE).
As priority, in step 8), the concentration of the thioacetamide is maintained at 0.01-1mol/L.
As priority, in step 12) for carbon-coated carbon source be glucose, phenolic resin, ethylene glycol one kind or
It is a variety of.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1, composite material pattern prepared by the present invention is rodlike, and rodlike composite material is by graphene portion envelops, each stick
It is together in series by graphene between shape composite material, not by the rodlike composite material of graphene wrapping portion by carrying out surface two
Secondary high temperature carbon coating so that all rodlike ferrimanganic sulfur graphite alkene composite materials can be in the dual work of graphene and carbon coating layer
Under, a complete conductive network is formed；The stomata that graphene surface is generated with potassium hydroxide high-temperature heat treatment simultaneously makes
Each rodlike composite material can reserve enough channels for electrolyte infiltration and ion transmission in electrochemical reaction；
2, since graphene surface produces stomata so that transition metal iron manganese sulfide and porous graphene are compound, more
Hole graphene wrapping material for rod-like ferrimanganic sulfide is connected by graphene between each club-shaped material, and conductive structure is formed, so as to
Deficiency of the metal sulfide in terms of diffusion and conductibility is made up to send out using the big specific surface of graphene and conductive performance
Wave its fake capacitance property；Because of the case where failing fully wrapped around rodlike ferrimanganic sulfide there are graphene, to rodlike ferrimanganic
Sulfide graphene composite material carries out carbon coating processing, and graphene is failed to fully wrapped around rodlike ferrimanganic sulfide composite wood
Material carries out secondary cladding, is not only connected by graphene between rodlike ferrimanganic sulfide composite material, but also outside composite material
Portion's cladding carbon-coating to connect between all materials, ultimately forms a complete conductive network, this structure can
Internal resistance of the composite material as electroactive material is effectively reduced, the conductivity of composite material is further increased, accelerates electrochemistry
The transmission of electronics during reaction is constituted；On the other hand, carbon coating to composite material the electroactive material in electro-chemical test cyclic process
The expansion or contraction of material play a certain protective role, and enhance the structural stability of composite material, it is made to show well
Cyclical stability；
3, the double protection structures of the graphene package, carbon layer on surface cladding that are formed, effectively reduce rodlike ferrimanganic sulfide
Graphene composite material during multiple reversible reaction great specific surface area collapse and the reunion of electroactive material, have
Help improve the electrochemical cycle stability of the composite material；
4, the ternary ferrimanganic sulfur graphite alkene composite material using two one-step hydrothermals prepare, by washing obtain the first step,
Drying is not needed after second step hydrothermal product；First step hydrothermal product is dry to be avoided product and causes in the drying process
Graphene shrink, to being avoided in second step hydrothermal reaction process since first step product is wrapped up in the contraction of graphene
Excessively tightly hinder the formation of ternary ferrimanganic sulfide in second step hydrothermal reaction process；Second step hydro-thermal reaction product is washing
Appropriate amount of deionized water is added later and carbon source is transferred to progress high temperature carbon coating in quartz boat later so that graphene and carbon coating
Close adhesion between layer, graphene and club-shaped material, carbon coating layer and club-shaped material, forms firm conductive network structure.
Description of the drawings
1 ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Fig. 1 embodiments；
1 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Fig. 2 embodiments；
1 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure partial sweep electron microscope of Fig. 3 embodiments；
2 ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Fig. 4 embodiments；
2 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Fig. 5 embodiments；
2 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure partial sweep electron microscope of Fig. 6 embodiments；
3 ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Fig. 7 embodiments；
3 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Fig. 8 embodiments；
3 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure partial sweep electron microscope of Fig. 9 embodiments；
4 ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Figure 10 embodiments；
4 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure scanning electron microscope (SEM) photograph of Figure 11 embodiments；
4 carbon coating ternary ferrimanganic sulfide graphene composite material appearance structure partial sweep electron microscope of Figure 12 embodiments；
The electrochemistry loop test performance curve of Figure 13 embodiment of the present invention 1；
The electrochemistry loop test performance curve of Figure 14 embodiment of the present invention 2；
The electrochemistry loop test performance curve of Figure 15 embodiment of the present invention 3；
The electrochemistry loop test performance curve of Figure 16 embodiment of the present invention 4.
Specific implementation mode
The present invention is further illustrated in the following with reference to the drawings and specific embodiments, and graphene solution used is and hydrogen
Potassium oxide is uniformly mixed the graphene solution prepared after high-temperature process makes graphene surface generate stomata.
It elaborates to the present invention with reference to Fig. 1-Figure 16.
Embodiment 1
A kind of synthetic method of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, including walk as follows
Suddenly：
1) graphene for measuring the manganese nitrate solution 1ml, 1g/L of the iron nitrate solution 4ml, 0.5mol/L of 0.5mol/L is molten
Liquid 20ml, graphene solution are to be prepared after graphene and KOH heat treatments under 500 DEG C of high temperature, are sufficiently stirred 10min；
2) it weighs ammonium fluoride solid 50mg to be added in above-mentioned mixed solution, stirs 10min；
3) it weighs urea 150mg to be added in above-mentioned mixed solution, stirs 20min；
4) aforesaid liquid is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
5) hydro-thermal reaction, reaction time 10h are carried out at 180 DEG C；
6) taking precipitate is filtered washing or centrifuge washing for several times；
7) 25ml deionized waters are added in 6) in sediment, weighs 200mg thioacetamide solids and above-mentioned solution is added
In, stir 20min；
8) 7) liquid in is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
9) hydro-thermal reaction, reaction time 10h are carried out at 90 DEG C；
10) taking precipitate is filtered washing or centrifuge washing for several times, you can obtains club shaped structure ternary ferrimanganic sulphur stone
Black ene compound composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 1；
11) 10) 20ml deionized waters are added in sediment in, 10mg ethylene glycol powder is added, ultrasonic disperse is uniform, transfer
To in high temperature process furnances in N2It protects lower 450 DEG C of sintering 1h to carry out carbon coating, obtains carbon coating club shaped structure ternary ferrimanganic sulphur
Compound graphene composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 2,3, it is known that compared to club shaped structure ternary ferrimanganic
The pattern of sulfur graphite ene compound composite material, carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material is more dredged
Pine.
No carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material manufactured in the present embodiment as shown in Figure 1,
Show that nanorod length is about 650nm, width is about that 240nm, Fig. 2 and Fig. 3 show the club shaped structure carried out after carbon coating
The shape appearance figure of ternary ferrimanganic sulfur graphite alkene composite material, it can be seen that on its pattern be club shaped structure, be carry out carbon coating after,
Club-shaped material it is smaller, it is interlaced so that can be firmer and fluffy between composite material with the adherency of graphene
Degree increases；As shown in figure 13, it is tested by electrochemistry cycle performance, its specific capacity retention is after 2000 cycles
94.9%, only decay 5.1%.
Embodiment 2
A kind of synthetic method of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, including walk as follows
Suddenly：
1) graphene solution of the manganese nitrate solution 4ml, 1g/L of the iron nitrate solution 4ml, 0.5mol/L of 1mol/L are measured
20ml, graphene solution are to be prepared after graphene and KOH heat treatments under 500 DEG C of high temperature, are sufficiently stirred 10min；
2) it weighs ammonium fluoride solid 100mg to be added in above-mentioned mixed solution, stirs 10min；
3) it weighs urea 150mg to be added in above-mentioned mixed solution, stirs 20min；
4) aforesaid liquid is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
5) hydro-thermal reaction, reaction time 10h are carried out at 180 DEG C；
6) taking precipitate is filtered washing or centrifuge washing for several times；
7) 25ml deionized waters are added in 6) in sediment, weighs 350mg thioacetamide solids and above-mentioned solution is added
In, stir 20min；
8) 7) liquid in is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
9) hydro-thermal reaction, reaction time 10h are carried out at 100 DEG C；
10) taking precipitate is filtered washing or centrifuge washing for several times, you can obtains club shaped structure ternary ferrimanganic sulphur stone
Black ene compound composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 4；
11) 10) 20ml deionized waters are added in sediment in, 15mg glucose powder is added, ultrasonic disperse is uniform, transfer
To in high temperature process furnances in N2It protects lower 500 DEG C of sintering 3h to carry out carbon coating, obtains carbon coating club shaped structure ternary ferrimanganic sulphur
Compound graphene composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 5,6, it is known that compared to club shaped structure ternary ferrimanganic
Sulfur graphite ene compound composite material, carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, is more evenly distributed.
No carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material manufactured in the present embodiment as shown in figure 4,
Show that nanorod length is about 1 μm, width is 200nm or so.Fig. 5 and Fig. 6 show the club shaped structure three carried out after carbon coating
The shape appearance figure of first ferrimanganic sulfur graphite alkene composite material, it can be seen that it is club shaped structure on its pattern, but after carrying out carbon coating,
Club-shaped material it is smaller, it is interlaced so that can be firmer and loose between composite material with the adherency of graphene
Degree increases；As shown in figure 14, it is tested by electrochemistry cycle performance, its specific capacity retention is after 2000 cycles
91.4%, decaying 8.6%.
Embodiment 3
A kind of synthetic method of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, including walk as follows
Suddenly：
1) graphene solution of the manganese nitrate solution 4ml, 2g/L of the iron nitrate solution 4ml, 1mol/L of 3mol/L are measured
15ml, graphene solution are to be prepared after graphene and KOH heat treatments under 800 DEG C of high temperature, are sufficiently stirred 10min；
2) it weighs ammonium fluoride solid 100mg to be added in above-mentioned mixed solution, stirs 10min；
3) it weighs urea 300mg to be added in above-mentioned mixed solution, stirs 20min；
4) aforesaid liquid is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
5) hydro-thermal reaction, reaction time 10h are carried out at 120 DEG C；
6) taking precipitate is filtered washing or centrifuge washing for several times；
7) 25ml deionized waters are added in 6) in sediment, weighs 500mg thioacetamide solids and above-mentioned solution is added
In, stir 20min；
8) 7) liquid in is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
9) hydro-thermal reaction, reaction time 10h are carried out at 100 DEG C；
10) taking precipitate is filtered washing or centrifuge washing for several times, you can obtains club shaped structure ternary ferrimanganic sulphur stone
Black ene compound composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 7；
11) 10) 20ml deionized waters are added in sediment in, 20mg glucose powder is added, ultrasonic disperse is uniform, transfer
To in high temperature process furnances in N2It protects lower 550 DEG C of sintering 3h to carry out carbon coating, obtains carbon coating club shaped structure ternary ferrimanganic sulphur
Compound graphene composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 8,9, it is known that compared to club shaped structure ternary ferrimanganic
The pattern of sulfur graphite ene compound composite material, carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material is more equal
It is even.
No carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material manufactured in the present embodiment as shown in fig. 7,
Show that nanorod length is about 667nm, width is about that 133nm, Fig. 8 and Fig. 9 show the club shaped structure carried out after carbon coating
The shape appearance figure of ternary ferrimanganic sulfur graphite alkene composite material, it can be seen that on its pattern be club shaped structure, but carry out carbon coating it
Afterwards, club-shaped material is smaller, interlaced so that the adherency with graphene can be firmer, and between composite material
Porousness increases；As shown in figure 15, it is tested by electrochemistry cycle performance, its specific capacity retention is after 2000 cycles
92.1%, decaying 7.9%.
Embodiment 4
A kind of synthetic method of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, including walk as follows
Suddenly：
1) graphene for measuring the manganese nitrate solution 1ml, 1g/L of the iron nitrate solution 4ml, 0.5mol/L of 0.5mol/L is molten
Liquid 20ml, graphene solution are to be prepared after graphene and KOH heat treatments under 800 DEG C of high temperature, are sufficiently stirred 10min；
2) it weighs ammonium fluoride solid 2.5mmol to be added in above-mentioned mixed solution, stirs 10min；
3) it weighs urea 2.5mmol to be added in above-mentioned mixed solution, stirs 20min；
4) aforesaid liquid is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
5) hydro-thermal reaction is carried out at 120 DEG C, the reaction time is for 24 hours；
6) taking precipitate is filtered washing or centrifuge washing for several times；
7) 25ml deionized waters are added in 6) in sediment, weighs 2mmol thioacetamide solids and above-mentioned solution is added
In, stir 20min；
8) 7) liquid in is transferred in the polytetrafluoroethyllining lining of 50ml reaction kettles and is sealed；
9) hydro-thermal reaction, reaction time 10h are carried out at 100 DEG C；
10) taking precipitate is filtered washing or centrifuge washing for several times, you can obtains club shaped structure ternary ferrimanganic sulphur stone
Black ene compound composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 10；
11) 10) 20ml deionized waters are added in sediment in, 25mg ethylene glycol powder is added, ultrasonic disperse is uniform, transfer
To in high temperature process furnances in N2It protects lower 750 DEG C of sintering 3h to carry out carbon coating, obtains carbon coating club shaped structure ternary ferrimanganic sulphur
Compound graphene composite material, appearance structure scanning electron microscope (SEM) photograph are as shown in Figure 11,12, it is known that compared to three rod iron of club shaped structure
Manganese sulfur graphite ene compound composite material, the pattern of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material is more
It is loose.
No carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material manufactured in the present embodiment is as shown in Figure 10,
Show that nanorod length is about 760nm, width is about that 120nm, Figure 11 and Figure 12 show the rodlike knot carried out after carbon coating
The shape appearance figure of structure ternary ferrimanganic sulfur graphite alkene composite material, it can be seen that be club shaped structure on its pattern, but carry out carbon coating
Later, club-shaped material is smaller, interlaced so that the adherency with graphene can be firmer, and between composite material
Porousness increase；As shown in figure 16, it is tested by electrochemistry cycle performance, its specific capacity retention after 2000 cycles
It is 91.6%, only decays 8.4%.
The above, only presently preferred embodiments of the present invention, are not intended to limit the invention, patent protection model of the invention
It encloses and is subject to claims, equivalent structure variation made by every specification and accompanying drawing content with the present invention, similarly
It should be included within the scope of the present invention.
Claims (10)
1. a kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, it is characterised in that：The composite material
Sandwich layer be club shaped structure ternary ferrimanganic sulfide, the ternary ferrimanganic sulfide is coated with graphene layer, and rodlike knot
It is connected through graphene layer between the ternary ferrimanganic sulfide of structure, ternary ferrimanganic sulfide corresponds to the position not coated by graphene layer
It is coated with carbon coating layer, composite material forms complete conductive network, institute under the double action of graphene layer and carbon coating layer
The stomata of connection ternary ferrimanganic sulfide is distributed in the surface for stating graphene layer.
2. a kind of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as described in claim 1, feature
It is：The ternary ferrimanganic sulfide of the club shaped structure is nanometer rods, and the length of nanometer rods is 100nm-5 μm, nanometer rods width
It is 10nm-1 μm.
3. a kind of synthetic method of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material, which is characterized in that packet
Include following steps：
1) graphene and potassium hydroxide are mixed evenly in tube furnace, match graphene in 350-800 DEG C of pyroreaction
Graphene solution is made；
2) ferric nitrate, manganese nitrate solution are then measured, graphene solution is added, is sufficiently stirred 10min；
3) it weighs in the above-mentioned mixed solution of ammonium fluoride solid addition and stirs 10min；
4) it weighs in the above-mentioned mixed solution of urea addition and stirs 20min；
5) aforesaid liquid is transferred in reaction kettle or other corresponding vessel and is sealed；
6) reactions such as hydro-thermal or water-bath, reaction time 5-24h are carried out at 90-200 DEG C；
7) taking precipitate is filtered washing or centrifuge washing；
8) it weighs deionized water and product that thioacetamide obtains in 7), is sufficiently stirred 20min；
9) 8) liquid obtained is transferred in reaction kettle or other corresponding vessel and is sealed；
10) reactions such as hydro-thermal or water-bath, reaction time 5-24h are carried out at 90-200 DEG C；
11) taking precipitate is filtered washing or centrifuge washing obtains clean product, you can obtains club shaped structure ternary ferrimanganic
Sulfur graphite ene compound composite material；
12) in 300-800 DEG C of N21-5h high temperature sintering carbon coatings are carried out under environment, obtain carbon coating club shaped structure ternary ferrimanganic
Sulfide graphene composite material.
4. a kind of synthesis side of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：A concentration of 0.1-3g/L of graphene solution in the step 1).
5. a kind of synthesis side of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：In the step 2) ferric nitrate, manganese nitrate solution, Fe3+Mole be Mn2+1-6 times, wherein nitric acid
A concentration of 0.1-5mol/L of iron.
6. a kind of synthesis side of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：In step 3), after ammonium fluoride solid is added in mixed solution, fluorination ammonium concentration is maintained at 0.01-3mol/
L。
7. a kind of synthesis side of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：In step 4), after urea is added in mixed solution, the concentration of urea is maintained at 0.01-5mol/L.
8. a kind of synthesis side of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：The material of step 5), step 9) reaction kettle or other corresponding vessel is polytetrafluoroethylene (PTFE).
9. a kind of synthesis side of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：In step 8), the concentration of the thioacetamide is maintained at 0.01-1mol/L.
10. a kind of synthesis of carbon coating club shaped structure ternary ferrimanganic sulfide graphene composite material as claimed in claim 3
Method, it is characterised in that：One kind or more that carbon-coated carbon source is glucose, phenolic resin, ethylene glycol is used in step 12)
Kind.
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